Search

The characterization of spilled petroleum products in an oil spill is necessary for identifying the spill source, selection of clean-up strategies, and evaluating potential environmental and ecological impacts. Existing standard methods for the chemical characterization of spilled oils are time-consuming due to the lengthy sample preparation for analysis. The main objective of this study is the development of a rapid screening method for the fingerprinting of spilled petroleum products using excitation/emission matrix (EEM) fluorescence spectroscopy, thereby delivering a preliminary evaluation of the petroleum products within hours after a spill. In addition, the developed model can be used for monitoring the changes of aromatic compositions of known spilled oils over time. This study involves establishing a fingerprinting model based on the composition of polycyclic and heterocyclic aromatic hydrocarbons (PAH and HAHs, respectively) of 130 petroleum products at different states of evaporative weathering. The screening model was developed using parallel factor analysis (PARAFAC) of a large EEM dataset. The significant fluorescing components for each sample class were determined. After which, through principal component analysis (PCA), the variation of scores of their modeled factors was discriminated based on the different classes of petroleum products. This model was then validated using gas chromatography-mass spectrometry (GC-MS) analysis. The rapid fingerprinting and the identification of unknown and new spilled oils occurs through matching the spilled product with the products of the developed model. Finally, it was shown that HAH compounds in asphaltene and resins contribute to ≥4-ring PAHs compounds in petroleum products.

The occurrence, spatial distribution and source of petroleum-related hydrocarbons, and the degree of weathering of Arrow oil residues persisting on the shoreline of Chedabucto Bay, Nova Scotia, were assessed. The hydrocarbons assessed included total petroleum hydrocarbons (TPH), n-alkanes from n-C9 to n-C40, petroleum biomarkers like terpanes, hopanes and steranes, non-alkylated polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues (APAHs). Trapped Arrow oil in the sunken tanker has not experienced any marked weathering. The collected environmental samples could be classified into three groups. Group 1 samples were oil free identified by low TPH, highly resolved fractions, a predominantly biogenic source of n-alkanes, and trace amounts of petroleum biomarkers probably from the historical (1970) oil spill. Group 2 samples had higher TPH and the other targets than Group 1 samples. The mixed petrogenic and terrestrial plant inputs were the source of n-alkanes, while the pattern of APAHs indicated that their source varied from site to site, being either recently released petroleum or Arrow oil residues. Group 3 samples mainly contained oil residues from Arrow oil spill, having very high levels of TPH, APAHs and biomarkers; however, most samples were free of n-alkanes. Group 3 samples were mostly found on the southern shoreline of Chedabucto Bay, especially in the upper to middle intertidal zone of the shorelines characterized by mixed pebble/cobble/boulders. The extent of weathering of n-alkanes and APAHs showed no relation to each other, although n-alkanes were depleted more fully than APAHs for most of the oil residues. Thus, various natural attenuation processes, especially for microbial degradation, have contributed to the aging of these oil residues. The degree of weathering varied with different environmental conditions.

In this study, the water accommodated and particle-laden hydrocarbon species, and the toxicity of the aqueous phase after oil-sediment interactions by varying the weathering states of diluted bitumen (Cold Lake blend (CLB)), oil type from light to heavy, and sediment type. Compared to the original oils, the sediment-laden total petroleum hydrocarbons (TPH) contained fewer hydrocarbons in the carbon range C34 range. Sediment-laden oil amounts generally decreased with an increased viscosity and asphaltene content of the test oils, as well as with increased sediment particle size. The presence of sediments significantly decreased the oil accommodated in water due to the formation of oil particulate aggregates (OPA) after mixing and settling. Less water accommodated TPH and polycyclic aromatic hydrocarbons (PAHs) were observed for weathered CLB products. However, oil and sediment types did not clearly affect the water accommodated TPH and PAHs. Light molecular PAHs and their alkylated congeners accounted for most of the water accommodated PAH congeners. A microtoxicity test demonstrated that with or without sediment, and regardless of sediment type, the toxicity of the water phase did not change significantly. Light oil of Alberta sweet mixed blend (ASMB) had the highest toxicity, followed by fresh CLB, and then all other oils, suggesting that ASMB and fresh CLB had relatively higher levels of light toxic components dissolved in the water phase compared with the other tested oils.

The Fraser River Delta is a unique and dynamic region supporting the diverse ecosystems and habitats in the Canadian West Coast. Total petroleum hydrocarbons (TPH), n-alkanes, petroleum biomarkers, and polycyclic aromatic hydrocarbons (PAHs) were analyzed for the intertidal sediments taken from the shorelines of the Delta area, British Columbia, Canada, to establish the baseline background data. Most of the sampling sites had low TPH (< 40 μg/g); only two samples had TPH from 100 to 150 μg/g. Mainly biogenic n-alkanes were present in all sites. Non-detectable to trace amounts of petroleum biomarkers were found at most sites. Mixed pyrogenic and petrogenic inputs contributed to the presence of PAHs at most sites. PAHs are not present in amounts anticipated negative effects to benthic organisms in all sampling sites, except that benzo (a) pyrene (BaP) from the upper intertidal zone (UIZ) of Burnaby Fraser Foreshore Park may have possible adverse biological effects.

The ability to characterize the composition of emerging unconventional Bakken tight oil is essential to better prepare for potential spills and to assess associated environmental concerns. The present work measured and compared the physical and chemical properties of Bakken crudes with conventional crude oils from various regions and different types of refined petroleum products. The physicochemical properties of Bakken crude are overall similar to those of conventional light crudes. The Bakken crude consists of high concentrations of monoaromatic hydrocarbons and alkylated PAHs with a clear dominance of the alkylated naphthalene homologues followed by the phenanthrene series. Its pyrogenic index (PI) values are considerably lower than typical conventional crude oils. The Bakken crude oils in this study exhibit a low abundance of petroleum biomarker such as terpanes, steranes and diamondoids and bicyclic sesquiterpanes. Since tight oil from the Bakken region is produced from low-permeability formations, variations in abundance and diagnostic ratios of common target petroleum hydrocarbons were found among these oils.

Following the 16TAN Husky oil spill along the North Saskatchewan River (NSR), the occurrence and natural attenuation of the petroleum hydrocarbons were assessed by analyzing the littoral zone sediments/oil debris collected from July 2016 to October 2017. Husky oil-free, mixed sediment-Husky oil, and Husky oil debris samples were identified for all the collected samples. Shoreline sediments were contaminated by mixed biogenic, pyrogenic and petrogenic inputs prior to the spill. Oil stranded on the shoreline of NSR was moved or buried due to the very dynamic conditions of the shoreline, or cleaned through a series of cleanup activities after the spill. Most normal alkanes were naturally weathered, whereas most of the branched alkanes and all of the saturated petroleum biomarkers remained. Some lighter molecular weight (e.g., 2 to 3-ring) polycyclic aromatic hydrocarbons (PAHs) were lost rapidly after the spill, whereas sulfur containing components, e.g., dibenzothiophenes and benzonaphthothiiophenes, and those having a heavier molecular weight did not change markedly even 15 months post-spill. Similarly, some light hydrocarbons (e.g.

This paper summarizes the results of the decontamination of the infrastructure materials concrete, limestone, brick and asphalt contaminated with 60Co, 85Sr, 137Cs and 241Am. The paper focuses on the effect of differences in substrate properties and of the pH of the radionuclide solution used for surface contamination on adsorption or ion exchange of the radionuclides and how these factors affect the decontamination effectiveness. A six-component chemical formulation was used and a process effectiveness of up to 76% was obtained depending on the substrate and radionuclide. Asphalt was the easiest material to decontaminate because of its more hydrophobic nature. Concrete and limestone (and to some extent brick) were less effectively decontaminated as their porous surfaces allowed penetration of radionuclides into water-filled pores in the substrate facilitating adsorption or ion exchange and making them difficult to remove. Brick was the most difficult material to decontaminate because the major component of brick is clay which retains most mono- and divalent ions. The removal of 60Co, 85Sr and 137Cs from the surfaces of concrete, limestone and brick increased when the pH of the radionuclide solutions was moderately acidic to neutral compared to when they were highly acidic. The variability in the test results was similar to that observed in other studies using other decontamination methods, attributed to the inhomogeneity of the substrates used and considered representative of real infrastructure materials.

The fate and behavior of diluted bitumen spilled in marine conditions has recently become a topic of much interest, yet, only limited knowledge is available. One of the major issues of a diluted bitumen spill on water is whether the product will sink, especially when suspended sediment is present in the water column. This study demonstrated how weathering processes influenced the key spill-related properties of a diluted bitumen product (Cold Lake Blend-Winter), and how interaction of diluted bitumen with sediment affected its tendency to float or sink in water. This study showed that the weathering states of the oils as well as the size of sediment are important factors influencing oil-sediment interactions and the tendency of the formed oil-particulate aggregates for buoyancy. When mixing with fine- and medium-sized sediments, the fresh to moderately weathered oils formed oil-particulate aggregates and sank in saltwater, while the very heavily-weathered oil formed discrete free-floating tarballs.

Perfluorinated compounds (PFCs) are emerging environmental pollutants. Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are the two primary PFC contaminants that are widely found in water, particularly in groundwater. This study compared the adsorption behaviors of PFOS and PFOA on several commercially available adsorbents in water. The tested adsorbents include granular activated carbon (GAC: Filtrasorb 400), powdered activated carbon, multi-walled carbon nanotube (MCN), double-walled carbon nanotube, anion-exchange resin (AER: IRA67), non-ion-exchange polymer, alumina, and silica. The study demonstrated that adsorption is an effective technique for the removal of PFOS/PFOA from aqueous solutions. The kinetic tests showed that the adsorption onto AER reaches equilibrium rapidly (2 h), while it takes approximately 4 and 24 h to reach equilibrium for MCN and GAC, respectively. In terms of adsorption capacity, AER and GAC were identified as the most effective adsorbents to remove PFOS/PFOA from water. Furthermore, MCN, AER, and GAC proved to have high PFOS/PFOA removal efficiencies (≥98%). AER (IRA67) and GAC (Filtrasorb 400) were thus identified as the most promising adsorbents for treating PFOS/PFOA-contaminated groundwater at mg L−1 level based on their equilibrium times, adsorption capacities, removal efficiencies, and associated costs.

The technical aspects of oil spill remote sensing are examined and the practical uses and drawbacks of each technology are given with a focus on unfolding technology. The use of visible techniques is ubiquitous, but limited to certain observational conditions and simple applications. Infrared cameras offer some potential as oil spill sensors but have several limitations. Both techniques, although limited in capability, are widely used because of their increasing economy. The laser fluorosensor uniquely detects oil on substrates that include shoreline, water, soil, plants, ice, and snow. New commercial units have come out in the last few years. Radar detects calm areas on water and thus oil on water, because oil will reduce capillary waves on a water surface given moderate winds. Radar provides a unique option for wide area surveillance, all day or night and rainy/cloudy weather. Satellite-carried radars with their frequent overpass and high spatial resolution make these day–night and all-weather sensors essential for delineating both large spills and monitoring ship and platform oil discharges. Most strategic oil spill mapping is now being carried out using radar. Slick thickness measurements have been sought for many years. The operative technique at this time is the passive microwave. New techniques for calibration and verification have made these instruments more reliable.

JOURNAL OF CONTEMPORARY WATER RESEARCH & EDUCATION There are approximately 52,000 “community” water systems (Rourke and Selby 2002) and 16,000 “publicly owned treatment works” or wastewater systems (U.S. Environmental Protection Agency 2002b) in the United States. While the vast majority of water and sewer customers are served by large metropolitan systems, most systems are small and located in rural areas. Due to their small size, these rural systems are generally more expensive to build and operate on a per-user basis, and they tend to have more problems complying with environmental and public health requirements. Many of these systems need special help to serve their customers reliably over the long term. Within the last few years, the U.S. Environmental Protection Agency (EPA) commissioned two studies of community water systems. One was the Community Water System Survey 2000 (Rourke and Selby 2002); the other was the Clean Water and Drinking Water Infrastructure Gap Analysis (U.S. Environmental Protection Agency 2002a), commonly referred to as the Gap Analysis. These studies revealed that between the years 2000 and 2020 water and sewer systems in the U.S. will experience a cumulative funding shortfall for operating and capital improvement costs of between 500 and 750 billion dollars. We are now several years into that time frame, and there is little evidence of progress toward erasing the looming shortfall. Without measures to increase revenues and reduce costs, in the next several decades, our water and sewer systems will experience serious financial upsets that may shut some systems down and seriously imperil the operations of many others. The effects will hit small rural systems disproportionately hard. Large systems enjoy economies of scale that allow them to hire financial and other management and planning expertise. They tend to be well funded and managed on a current operations basis. However, they will experience a staggering capital improvements funding shortfall over the next few decades as they replace aging distribution and treatment systems. Small systems, lacking economies of scale, are frequently poorly funded. They will experience the same kinds of funding shortfalls as the large systems. They also commonly operate at a loss on an operating cost basis. Small system managers attempt to manage well, but they are at a distinct disadvantage without proper training, experience, tools, and funding. This paper examines successes in helping small systems, and it highlights opportunities to strengthen the capacity of these systems.

The goal of this study was to investigate the usefulness of cyclodextrins (CDs) for the removal of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzo furans (PCDDs/PCDFs) in soil and water. Five CDs having different molecular cavities and active functional groups were selected and evaluated for their ability to include (trap) PCDDs/PCDFs in soil and water. For the soil experiments, CDs were added to the soil on day one and the concentrations of unbound PCDDs/PCDFs were monitored over a 28-day period. Parallel control experiments were conducted to assist in the process performance evaluation. The ability of CDs to remove PCDDs/PCDFs from the contaminated soil was dependent upon the type of CD used and constituents of PCDDs/PCDFs. Among the five CDs investigated, hydroxypropyl-β -cyclodextrin (HPBCD) gave the highest removal efficiency for all components of PCDDs/PCDFs. The removal efficiency of total PCDDs/PCDFs was 81% one day after application of CDs and then increased to 96% after 28 days. Th...

In this study, a "green chemistry" approach was developed as an option for remediation of toxic mercury in the environment. Twenty mercury compounds were treated with an environmentally friendly agent cyclodextrin to produce stable non-toxic mercury in soil and water. The binding efficiency was determined using high performance liquid chromatography with diode-array detection. The stability of the cyclodextrin mercury complexes toward environmental microorganisms in water was estimated under OECD guidelines using gas chromatography-mass spectrometry. The toxicity of the cyclodextrin mercury compounds to terrestrial organisms was investigated by use of internationally recognized toxicity methods using mercuric acetate as a model contaminant. Key process conditions, for example pH, temperature, and amount of detoxifying agent were investigated and found to have significant effects on the toxicity of mercury. It was found that organic and inorganic mercury pollutants could be mineralized in the environment with cyclodextrins. The bound mercury compounds resisted biodegradation and were found to be non-toxic to environmental microorganisms under laboratory conditions.

A forensic identification method based on the chemical fingerprinting of the first generation of biodiesel (fatty acid alkyl esters as effective components), and several corresponding diagnostic ratios was developed and validated. The distribution of major fatty acid methyl esters (FAMEs) and polar compounds (free fatty acids, glycerol, monoacylglycerides, and free sterols) in several representative above biodiesel products commercially available in Canada were positively quantified and compared, a number of cross-plots of diagnostic ratios of target FAMEs and sterols were developed for biofuel correlation and differentiation. It was found that the cross-plots of FAME ratios, for example, the sum of the di-unsaturated relative to saturated homologues of FAMEs (D/S) versus the sum of the mono-saturated to saturated FAMEs (M/S), and the sum of di-unsaturated to mono-saturated FAMEs (D/M) versus the sum of the mono-saturated to saturated FAMEs (M/S), could cluster samples clearly into their individual feedstock. The cross-plots of diagnostic ratios of individual major sterols (cholesterol, brassicasterol, campesterol, β-stiosterol and stigmasterol) to the total sterols were also developed and proved to be effective in identifying biodiesel sources due to their self-normalizing effect on sterol data. The case study of a mystery biodiesel spill using this method showed that the two real samples can be tightly clustered into biodiesel from animal fat (Ban) group. However, the significant discrepancy of free fatty acids, glycerol, monoacylglycerides and sterol concentrations between the two real samples indicated their different producing batches.

The continued demand for crude oil and related petroleum products along with the resulting upward spiral of the market price of oil have forced oil exploration and production companies to seek out new reserves farther offshore and in deeper waters. The United States is among the top five nations globally in terms of estimated offshore oil reserves and petroleum production. Yet deepwater drilling to extract these reserves is a major engineering challenge for oil companies. Moreover, such drilling activity also comes with a significant environmental risk, and the extremely high pressures associated with deepwater oil wells mean that the mitigation of accidental releases from a deepwater spill is truly a challenging endeavor.

A novel technique is described for monitoring transient infrared absorptions with a tunable diode laser (TDL). The technique involves modulating the TDL at frequencies as high as 250 kHz and using both analog and digital subtraction of background signals. Transient absorptions as small as 0.001% can be detected with a response time of a few microseconds. The technique provides excellent discrimination between transient absorption lines and spurious effects such as beam deflection. Transient detection of the CF(2) radical in a photolysis cell is used to illustrate the technique, and a comparison is made with more conventional TDL detection methods. The modulation technique is clearly a very powerful tool for transient infrared spectroscopy.

Laser magnetic resonance spectra of the OD radical in low-lying vibrational levels of the X 2 Π state have been recorded at a variety of wavelengths in the far-infrared. The spectra have been assigned to rotational and fine-structure transitions and fitted to a model Hamiltonian to determine the appropriate molecular parameters for the levels v = 0 to 3. The results are compared with those from previous studies of OD in these vibrational levels.

The infrared multiphoton dissociation (IRMPD) of "neat" hexafluoroethane has been investigated for the first time. The stable products of photolysis are CF4, C2F4, C3F8, and C4F10. Product analysis involved tunable diode laser (TDL) and fourier transform infrared spectroscopy, as well as gas chromatography where applicable. The high sensitivity and resolution of the TDL allows for measurement of the stable products CF4 and C2F4 after irradiation by a single infrared laser pulse. The yield of CF3 radicals produced by the IRMPD of C2F6 as a function of fluence was measured via the TDL high frequency modulation technique. The role of added H2, leading to elimination of CF4 and increase of C2F4 as products, is clarified.

The release of the organochlorine pesticide lindane (γ-hexachlorocyclohexane) from several types of contaminated building materials was studied to assess inhalation hazard and decontamination requirements in response to accidental and/or intentional spills. The materials included glass, polypropylene carpet, latex-painted drywall, ceramic tiles, vinyl floor tiles, and gypsum ceiling tiles. For each surface concentration, an equilibrium concentration was determined in the vapour phase of the surrounding air. Vapor concentrations depended upon initial surface concentration, temperature, and type of building material. A time-weighted average (TWA) concentration in the air was used to quantify the health risk associated with the inhalation of lindane vapors. Transformation products of lindane, namely α-hexachlorocyclohexane and pentachlorocyclohexene, were detected in the vapour phase at both temperatures and for all of the test materials. Their formation was greater on glass and ceramic tiles, compared to other building materials. An empiric Sips isotherm model was employed to approximate experimental results and to estimate the release of lindane and its transformation products. This helped determine the extent of decontamination required to reduce the surface concentrations of lindane to the levels corresponding to vapor concentrations below TWA.